Method for producing transition metal-isocyanide complex
11034712 · 2021-06-15
Assignee
- Kyushu University, National University Corporation (Fukuoka, JP)
- SHIN-ETSU CHEMICAL CO., LTD. (Tokyo, JP)
Inventors
- Hideo Nagashima (Fukuoka, JP)
- Atsushi Sanagawa (Fukuoka, JP)
- Daisuke Noda (Annaka, JP)
- Koji Sakuta (Annaka, JP)
Cpc classification
C07F11/00
CHEMISTRY; METALLURGY
International classification
C07F11/00
CHEMISTRY; METALLURGY
Abstract
This method is for producing a transition metal complex represented by formula (2), the method comprising reacting a compound containing a transition metal selected from V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, and Pt with an isocyanide compound represented by formula (1) in the presence of an alkali metal supported by a solid substance which is insoluble in an organic solvent. This production method can be used to easily and efficiently produce a transition metal complex that includes a predetermined transition metal having an oxidation number of 0 and that has the same or different isocyanide compounds, without using a compound harmful to the human body. (1): (CN).sub.x—R.sup.1 {R.sup.1 represents a mono- to tri-valent organic group having 1-30 carbon atoms, and x represents an integer of 1-3}. (2): M.sup.1.sub.a(L).sub.b {M.sup.1 represents V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, and is a zero-valent transition metal, L represents an isocyanide compound represented by formula (1), M.sup.1 and L may be the same or different from each other, “a” represents an integer of 1-8, and b represents an integer of 2-12}.
Claims
1. A method for producing a transition metal-isocyanide complex represented by formula (2) below, the method comprising reacting together a compound containing a transition metal selected from V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, and Pt, and an isocyanide compound represented by formula (1) below in the presence of an alkali metal supported by a solid substance insoluble in an organic solvent,
(CN).sub.x—R.sup.1 (1) wherein R.sup.1 represents a monovalent to trivalent organic group that has 1 to 30 carbon atoms and is optionally substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon are optionally interposed, and x represents an integer of 1 to 3,
M.sup.1.sub.a(L).sub.b (2) wherein M.sup.1 represents V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt with an oxidation number of zero, L represents an isocyanide compound represented by the formula (1), M.sup.1 may be the same or different, and L may be the same or different, “a” represents an integer of 1 to 8, and “b” represents an integer of 2 to 12, and wherein the solid substance insoluble in an organic solvent is at least one selected from a carbon material, a silicon compound, a metal oxide, and a polymer compound.
2. The method for producing a transition metal-isocyanide complex according to claim 1, wherein the compound containing a transition metal is at least one selected from a transition metal oxide, a transition metal acid or a salt thereof, and a halide salt, an oxyacid salt, a carboxylate, a sulfonate, an alkoxide salt, a β-diketonate, an amide salt, a tetrafluoroborate, or a hexafluorophosphate of the transition metal.
3. The method for producing a transition metal-isocyanide complex according to claim 1, wherein, in the formula (2), when a is 1, b is an integer of 2 to 6, when a is 2, b is an integer of 4 to 10, and when a is an integer of 3 to 8, b is an integer of 4 to 12.
4. The method for producing a transition metal-isocyanide complex according to claim 1, wherein, in the formula (1), x is 1.
5. The method for producing a transition metal-isocyanide complex according to claim 1, wherein, in the formula (2), M.sup.1 is Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt.
6. The method for producing a transition metal-isocyanide complex according to claim 1, wherein, in the formula (2), when a is 1, b is an integer of 2 to 6, when a is 2, b is an integer of 4, or 8 to 10, and when a is an integer of 3 to 8, b is 4, 6, 7, 10, or 12.
7. The method for producing a transition metal-isocyanide complex according to claim 1, wherein M.sup.1 in the formula (2) is Fe, Co, Rh, Ni, Pd, or Pt.
8. The method for producing a transition metal-isocyanide complex according to claim 1, wherein the compound containing a transition metal is a transition metal salt represented by formula (3) below,
M.sup.2X.sub.c (3) wherein M.sup.2 represents Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, X represents a halogen atom or a group represented by formula (4) below each of which is possibly the same as or different from another one, and c represents an integer of 1 to 6,
—OC(O)R.sup.2 (4) wherein R.sup.2 represents a monovalent organic group that has 1 to 30 carbon atoms and is optionally substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon are optionally interposed.
9. The method for producing a transition metal-isocyanide complex according to claim 8, wherein, in the formula (3), M.sup.2 is Fe, Co, Rh, Ni, Pd, or Pt.
10. The method for producing a transition metal-isocyanide complex according to claim 8 or 9, wherein R.sup.2 in the formula (4) is a monovalent hydrocarbon group having 1 to 30 carbon atoms.
11. The method for producing a transition metal-isocyanide complex according to claim 10, wherein R.sup.2 in the formula (4) is a methyl group.
12. The method for producing a transition metal-isocyanide complex according to claim 8, wherein X in the formula (3) is at least one selected from chlorine, bromine, and iodine.
13. The method for producing a transition metal-isocyanide complex according to claim 1, wherein R.sup.1 in the formula (1) is a monovalent hydrocarbon group having 1 to 30 carbon atoms.
14. The method for producing a transition metal-isocyanide complex according to claim 1, wherein R.sup.1 in the formula (1) is at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms.
15. The method for producing a transition metal-isocyanide complex according to claim 14, wherein R.sup.1 in the formula (1) is at least one hydrocarbon group selected from a t-butyl group, a 1-adamantyl group, a mesityl group, a phenyl group, a 2,6-dimethylphenyl group, and a 2,6-diisopropylphenyl group.
16. The method for producing a transition metal-isocyanide complex according to claim 1, wherein the solid substance insoluble in an organic solvent is at least one selected from graphite and silica gel.
17. The method for producing a transition metal-isocyanide complex according to claim 1, wherein the alkali metal is at least one selected from sodium, potassium, and sodium-potassium alloy.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
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DESCRIPTION OF EMBODIMENTS
(15) Below the invention is described in more detail.
(16) A method for producing a transition metal-isocyanide complex according to the present invention reacts together a compound containing a transition metal and an isocyanide compound represented by formula (1) in the presence of an alkali metal supported by a solid substance insoluble in an organic solvent.
(CN).sub.x—R.sup.1 (1)
(17) The transition metal used in the present invention is V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, preferably Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, and more preferably Fe, Co, Rh, Ni, Pd, or Pt.
(18) The compound containing any of these transition metals is not particularly limited as long as it can be reduced by being reacted with an alkali metal supported by a solid substance insoluble in an organic solvent, and examples include transition metal oxides; transition metal acids such as chloroplatinic acid and chloroauric acid, or salts thereof; transition metal oxyacid salts such as sulfates, carbonates, and phosphates; transition metal halide salts such as fluorides, chlorides, bromide salts, and iodides; transition metal alkoxide salts such as methoxides, ethoxides, and isopropoxides; transition metal carboxylates such as acetates, pivalates, and 2-ethylhexanoates; transition metal β-diketonates such as acetylacetonates; transition metal sulfonates such as p-toluenesulfonates and trifluoromethanesulfonates; transition metal amide salts such as bis(trimethylsilyl)amides; transition metal tetrafluoroborates; transition metal hexafluorophosphates; and the like; the compound is preferably a transition metal salt represented by formula (3) below.
M.sup.2X.sub.c (3)
(19) In formula (3), M.sup.2 represents Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, X represents a halogen atom or a group represented by formula (4) below, and c represents a number that changes in accordance with the oxidation number of the transition metal and represents an integer of 1 to 6.
—OC(O)R.sup.2 (4)
(20) In formula (4), R.sup.2 represents a monovalent organic group that has 1 to 30 carbon atoms and is optionally substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon are optionally interposed.
(21) Specific examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
(22) The monovalent to trivalent organic group having 1 to 30 carbon atoms is not particularly limited, but is preferably a monovalent to trivalent hydrocarbon group having 1 to 30 carbon atoms.
(23) Examples of monovalent hydrocarbon groups include alkyl, alkenyl, alkynyl, aryl, alkyl aryl, and aralkyl groups.
(24) The alkyl groups may be straight, branched or cyclic, is preferably 1 to 20, more preferably 1 to 10 alkyl group. Examples include straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosanyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, norbornyl, and adamantyl.
(25) The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and examples include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.
(26) The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, and examples include ethynyl, n-1-propynyl, n-2-propynyl, n-1-butynyl, n-2-butynyl, n-3-butynyl, 1-methyl-2-propynyl, n-1-pentynyl, n-2-pentynyl, n-3-pentynyl, n-4-pentynyl, 1-methyl-n-butynyl, 2-methyl-n-butynyl, 3-methyl-n-butynyl, 1,1-dimethyl-n-propynyl, n-1-hexynyl, n-1-decynyl, n-1-pentadecynyl, and n-1-eicosynyl.
(27) The aryl or alkylaryl group is preferably an aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms, and specific examples include phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, o-biphenylyl, m-biphenylyl, p-biphenylyl, tolyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, a mesityl group, and the like.
(28) The aralkyl group is an arylalkyl group preferably having 7 to 30 carbon atoms and more preferably having 7 to 20 carbon atoms, and specific examples include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, a naphthylpropyl group, and the like.
(29) Suitable divalent hydrocarbon groups include alkylene, arylene and aralkylene groups.
(30) The alkylene groups may be straight, branched or cyclic ones, preferably alkylene groups having 1 to 20 carbon atoms. Examples include straight or branched alkylene groups such as methylene, ethylene, propylene, trimethylene, n-butylene, isobutylene, s-butylene, n-octylene, 2-ethylhexylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, n-octadecylene, n-nonadecylene, and n-eicosanylene; and cycloalkylene groups such as 1,4-cyclohexylene.
(31) Examples of the arylene group include o-phenylene, m-phenylene, p-phenylene, 1,2-naphthylene, 1,8-naphthylene, 2,3-naphthylene, and 4,4′-biphenylene.
(32) Examples of the aralkylene group include —(CH.sub.2).sub.y—Ar— wherein Ar is an arylene group having 6 to 20 carbon atoms and y is an integer of 1 to 10, —Ar—(CH.sub.2).sub.y— wherein Ar and y are as defined above, and —(CH.sub.2).sub.y—Ar—(CH.sub.2).sub.y— wherein Ar is as defined above and y is each independently as defined above.
(33) Specific examples of the trivalent hydrocarbon group include those represented by the following formulae, but are not limited to these.
(34) ##STR00001##
(35) Specific examples of other organic groups in R.sup.2 above include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group; aryloxy groups such as a phenoxy group; alkyl halide groups such as a trifluoromethyl group; alkylamino groups such as a dimethylamino group; ester groups such as a methyl ester and an ethyl ester; a nitro group; a nitrile group; alkyl- or arylsilyl groups such as a trimethylsilyl group and a phenyldimethylsilyl group; alkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group; nitrogen-containing heterocycle-containing groups such as a pyridyl group; sulfur-containing heterocycle-containing groups such as a thienyl group; and the like.
(36) One or more atoms selected from oxygen, nitrogen, silicon, sulfur, and phosphorus may be interposed in each of the organic groups described above, and each of the organic groups described above may be substituted with a halogen atom.
(37) Among these, as R.sup.2, alkyl groups or cycloalkyl groups such as methyl, ethyl, n-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, stearyl, and a cyclohexyl group, and aryl groups such as a phenyl group are preferable, and a methyl group is more preferable.
(38) Specific examples of the compound containing a transition metal that can be used in the present invention are as follows.
(39) The iron salt includes iron halides such as FeCl.sub.2, FeBr.sub.2, FeCl.sub.3, FeBr.sub.3, and FeI.sub.3; iron carboxylates such as Fe(OAc).sub.2, Fe(stearate).sub.2, and Fe(stearate).sub.3; and the like.
(40) The cobalt salt includes cobalt halides such as CoCl.sub.2, CoBr.sub.2, and CoI.sub.2; cobalt carboxylates such as Co(OAc).sub.2, Co(benzoate).sub.2, Co(2-ethylhexanoate).sub.2, and Co(stearate).sub.2; and the like.
(41) The nickel salt includes nickel halides such as NiCl.sub.2, NiBr.sub.2, and NiI.sub.2; nickel carboxylates such as Ni(OAc).sub.2; and the like.
(42) As the ruthenium salt, ruthenium halides such as RuCl.sub.2 and RuCl.sub.3, and the like are given.
(43) As the rhodium salt, rhodium halides such as chloro(1,5-cyclooctadiene)rhodium (dimer) and RhCl.sub.3; rhodium carboxylates such as Rh.sub.2(OAc).sub.4; and the like are given.
(44) As the palladium salt, palladium halides such as PdCl.sub.2, PdBr.sub.2, and PdI.sub.2; palladium carboxylates such as Pd(OAc).sub.2; and the like are given.
(45) As the chromium salt, chromium halides such as CrCl.sub.2, CrCl.sub.3, and CrBr.sub.3; chromium carboxylates such as Cr(OAc).sub.2 and Cr(OAc).sub.3; and the like are given.
(46) As the molybdenum salt, molybdenum halides such as MoCl.sub.3 and MoCl.sub.5; molybdenum carboxylates such as Mo.sub.2(OAc).sub.4; and the like are given.
(47) As the tungsten salt, tungsten halides such as WCl.sub.6 and the like are given.
(48) As the vanadium salt, vanadium halides such as VCl.sub.2, VCl.sub.3, VBr.sub.3, and VI.sub.3, and the like are given.
(49) As the platinum salt, platinum halides such as PtCl.sub.2 and PtCl.sub.3; chloroplatinic acids such as H.sub.2PtCl.sub.6; chloroplatinates such as K.sub.2PtCl.sub.6; and the like are given.
(50) In particular, as the compound containing a transition metal in the present invention, halides such as chlorides, bromides, and iodides; and carboxylates such as acetates are preferable, and halides such as chlorides, bromides, and iodides are more preferable, in terms of reactivity with a reducing agent.
(51) In formula (3) above, a solvent or the like may be coordinated to M.sup.2. Examples of the solvent or the like include water; ammonia; amines such as ethyleneimine, N,N-tetramethylethylenediamine, and pyridine; ethers such as dimethoxyethane, diglyme, and tetrahydrofuran; nitriles such as acetonitrile and benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; olefins such as ethylene, 1,3-butadiene, 1,3-cyclohexadiene, cyclooctene, 1,5-cyclooctadiene, and norbornadiene; aromatic hydrocarbons such as benzene, toluene, and p-cymene; and the like.
(52) On the other hand, in formula (1) above, R.sup.1 represents a monovalent to trivalent organic group that has 1 to 30 carbon atoms and may be substituted with a halogen atom and in which one or more atoms selected from oxygen, nitrogen, sulfur, and silicon may be interposed, and x represents an integer of 1 to 3.
(53) As the monovalent to trivalent organic group having 1 to 30 carbon atoms, similar groups to those given as examples in the above are given; among them, a t-butyl group, a 1-adamantyl group, a mesityl group, a phenyl group, a 2,6-dimethylphenyl group, and a 2,6-diisopropylphenyl group are preferable as R.sup.1.
(54) x in formula (1) above represents an integer of 1 to 3, and is preferably 1 or 2 and more preferably 1.
(55) The isocyanide compound represented by formula (1) above may be obtained as a commercially available product, or may be synthesized by a known method. For example, it may be obtained by a method in which a formylated product is obtained from an amine compound and formic acid, and subsequently the formylated product is reacted with phosphoryl chloride in the presence of an organic amine to be turned into an isocyanide (Synthesis Method 1; see Organometallics, 2004, 23, 3976-3981); as a method for obtaining a formylated product under mild conditions, a formylated product can be obtained by forming acetic formic anhydride from acetic anhydride and formic acid, and reacting the acetic formic anhydride with an amine compound (Synthesis Method 2; see Org. Synth., 2013, 90, 358-366). The obtained formylated product can be turned into an isocyanide by the method described in Synthesis Method 1, which is the same as above.
(56) The synthesis can be made also by a method in which an amine compound and dichlorocarbene are reacted together to produce an isocyanide, which is a method not involving formylation (Synthesis Method 3; see Tetrahedron Letters, 1972, 17, 1637-1640).
(57) Examples of the isocyanide compound include alkyl isocyanides such as methyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropyl isocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentyl isocyanide, neopentyl isocyanide, n-hexyl isocyanide, cyclohexyl isocyanide, cycloheptyl isocyanide, 1,1-dimethylhexyl isocyanide, 1-adamantyl isocyanide, and 2-adamantyl isocyanide; aryl isocyanides such as phenyl isocyanide, 2-methylphenyl isocyanide, 4-methylphenyl isocyanide, 2,4-dimethylphenyl isocyanide, 2,5-dimethylphenyl isocyanide, 2,6-dimethylphenyl isocyanide, 2,4,6-trimethylphenyl isocyanide, 2,4,6-tri-t-butylphenyl isocyanide, 2,6-diisopropylphenyl isocyanide, 1-naphthyl isocyanide, 2-naphthyl isocyanide, 2-methyl-1-naphthyl isocyanide; aralkyl isocyanides such as benzyl isocyanide and phenylethyl isocyanide.
(58) Examples of the diisocyanide compound include 1,2-diisocyanoethane, 1,3-diisocyanopropane, 1,4-diisocyanobutane, 1,5-diisocyanopentane, 1,6-diisocyanohexane, 1,8-diisocyanooctane, 1,12-diisocyanododecane, 1,2-diisocyanocyclohexane, 1,3-diisocyanocyclohexane, 1,4-diisocyanocyclohexane, 1,3-diisocyano-2,2-dimethylpropane, 2,5-diisocyano-2,5-dimethylhexane, 1,2-bis(diisocyanoethoxy)ethane, 1,2-diisocyanobenzene, 1,3-diisocyanobenzene, 1,4-diisocyanobenzene, 1,1′-methylenebis(4-isocyanobenzene), 1,1′-oxybis(4-isocyanobenzene), 3-(isocyanomethyl)benzyl isocyanide, 1,2-bis(2-isocyanophenoxy)ethane, bis(2-isocyanophenyl)phenyl phosphonate, bis(2-isocyanophenyl) isophthalate, bis(2-isocyanophenyl) succinate.
(59) Examples of the triisocyanide compound include 1,3-diisocyano-2-(isocyanomethyl)-2-methylpropane, 1,5-diisocyano-3-(2-isocyanoethyl)pentane, 1,7-diisocyano-4-(3-isocyanopropyl)heptane, and 3-isocyano-N,N′-bis(3-isocyanopropyl)propane-1-amine.
(60) A transition metal-isocyanide complex of the present invention obtained by reacting together the compound containing a transition metal described above and the isocyanide compound represented by formula (1) above is represented by formula (2).
M.sup.1.sub.a(L).sub.b (2)
(61) In formula (2), M.sup.1 represents V, Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt with an oxidation number of zero; and is preferably Cr, Mo, W, Fe, Ru, Co, Rh, Ni, Pd, or Pt, and more preferably Fe, Co, Rh, Ni, Pd, or Pt. When there are a plurality of M.sup.1s, they may be the same or different.
(62) L represents the isocyanide compound represented by formula (1) above; when there are a plurality of L's, they may be the same or different.
(63) “a” represents an integer of 1 to 8, and “b” represents an integer of 2 to 12; from the viewpoints of the stability of the complex and catalytic activity, it is preferable that, when a is 1, b be an integer of 2 to 6; when a is 2, b be an integer of 4 to 10; when a is an integer of 3 to 8, b be an integer of 4 to 12; it is more preferable that, when a is 1, b be 2 to 6; when a is 2, b be an integer of 4, or 8 to 10; when a is an integer of 3 to 8, b be 6, 7, 10, or 12.
(64) In formula (2), L may be partially substituted with a known two-electron donating ligand, and a solvent or the like may be coordinated to L.
(65) The two-electron donating ligand refers to a neutral compound having an unpaired electron; and is not particularly limited as long as it is a ligand other than a carbonyl ligand, and may be a nitrogen molecule, an ether compound, an amine compound, a phosphine compound, a phosphite compound, a sulfide compound, or the like; in view of the stability of the compound, it is preferable that all L's be isocyanide compound ligands.
(66) As described above, in the present invention, the compound containing a transition metal mentioned above and the isocyanide compound represented by formula (1) above are reacted together in the presence of an alkali metal supported by a solid substance insoluble in an organic solvent.
(67) Here, the solid substance insoluble in an organic solvent is not particularly limited as long as it is a solid substance insoluble in an organic solvent used for reaction; examples include carbon materials such as activated carbon, graphite, carbon nanofibers, and carbon nanotubes; silicon compounds such as silicon; metal oxides such as zeolite, zinc oxide, ceria, silica gel, alumina, and titanium oxide; polymer compounds such as polystyrene; and the like.
(68) Specific examples of the alkali metal supported by a solid substance mentioned above include sodium, potassium, sodium-potassium alloy, and the like.
(69) The alkali metal supported by a solid substance insoluble in an organic solvent mentioned above is not particularly limited, and may be selected for use from conventionally known ones like those described in Patent Documents 1 to 5 and Non-Patent Documents 25 and 26 above, and the like, as appropriate; examples include sodium, potassium, or sodium-potassium alloy supported by silica, alumina, graphite, titanium oxide, zeolite, zinc oxide, cerium oxide, or polystyrene; among these, potassium-carrying graphite (hereinafter, abbreviated as KC.sub.8) is preferable from the viewpoint of reactivity, and sodium-carrying silica gel (Stage 1 or 2) is preferable in terms of low risk of ignitability etc. from the viewpoint of safety.
(70) These alkali metals supported by a solid substance insoluble in an organic solvent may be obtained as commercially available products; as such commercially available products, KC.sub.8 (manufactured by Strem Chemicals, Inc.), Na silica gel (manufactured by Aldrich Corporation, Stage I), Na silica gel (manufactured by Aldrich Corporation, Stage II), NaK.sub.2 silica gel (manufactured by Aldrich Corporation, Stage I), and the like are given.
(71) In the present invention, reaction conditions when producing a transition metal-isocyanide complex are not particularly limited.
(72) The reaction temperature is usually approximately 10 to 100° C., and preferably 20 to 80° C.; the period of reaction is approximately 1 to 48 hours.
(73) The reaction may be performed without a solvent, or may use an organic solvent in view of the control of the heat of reaction and the implementation of a post-treatment process after reaction.
(74) As an organic solvent, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylenes, and mesitylene; and the like can be used.
(75) The concentration of the reaction solution is not particularly limited, but the molar concentration (M) of the compound containing a transition metal is preferably 0.01 to 10 M and more preferably 0.01 to 2 M in view of the reactivity of the alkali metal supported by a solid substance insoluble in an organic solvent and the control of the heat of reaction.
(76) In the production of the transition metal-isocyanide complex of the present invention, the molar ratio of the isocyanide compound to the compound containing a transition metal is not particularly limited, but is preferably 2 to 20 equivalents, and more preferably 2 to 10 equivalents.
(77) Further, in the production of the transition metal-isocyanide complex of the present invention, the molar ratio of the alkali metal supported by a solid substance insoluble in an organic solvent to the compound containing a transition metal is not particularly limited, but is preferably 2 to 20 equivalents, and more preferably 2 to 8 equivalents.
(78) As the post-treatment process after reaction, the reducing agent may be removed by filtration using a glass filter, filter paper, or the like, and the organic solvent may be distilled off by heating and/or pressure reduction.
(79) The resulting compound may be used as it is, or may be purified by a known method. For example, the resulting compound may be cleaned with a solvent that the compound is insoluble or hardly soluble in, and may then be dried for use; alternatively, the resulting compound may be purified by reprecipitation or recrystallization by dissolving the compound in a good solvent and then performing cooling in this state, or by dissolving the compound in a good solvent and then adding a poor solvent that is diffusible in the good solvent.
EXAMPLES
(80) Examples are given below by way of illustration and not by way of limitation.
(81) All solvents were deoxygenated and dehydrated by well-known methods before they were used in the preparation of the compound containing a transition metal.
(82) The compound containing a transition metal obtained was stored in a nitrogen gas atmosphere at 25° C. until they were used in reaction.
(83) Hydrosilylation reaction and solvent purification of an alkene were always carried out in an inert gas atmosphere. The solvents and other ingredients were purified, dried and deoxygenated by well-known methods before they were used in various reactions.
(84) The measurement of .sup.1H-NMR was performed using JNM-ECA600 and JNM-LA400 manufactured by JEOL Ltd, and IR measurement was performed using FT/IR-550 manufactured by JASCO Corporation.
(85) In the chemical structure formulae shown below, hydrogen atoms are omitted in accordance with common expression. .sup.tBu represents a t-butyl group, Ad an adamantyl group, and Mes a mesityl group.
[Example 1] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.BU).SUB.8 .Using Cobalt Iodide and KC.SUB.8
(86) Cobalt iodide (0.31 g, 1.0 mmol), tetrahydrofuran (hereinafter, abbreviated as THF) (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 0.27 g, 2.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 40 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (0.24 g, yield: 61%). .sup.1H-NMR spectrum of the resulting complex is shown in
[Example 2] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Bromide and KC.SUB.8
(87) Cobalt bromide (22 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (33 mg, 0.40 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (27 mg, yield: 70%).
[Example 3] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Chloride and KC.SUB.8
(88) Cobalt chloride (13 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (33 mg, 0.40 mmol), and KC.sub.8 (27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, cobalt isocyanide complex Co.sub.2(CN.sup.tBu).sub.8 was obtained (27 mg, yield: 70%).
[Example 4] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Acetate and KC.SUB.8
(89) Cobalt acetate (18 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (33 mg, 0.40 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (4 mg, yield: 10%).
[Example 5] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CNAd).SUB.8 .Using Cobalt Iodide and KC.SUB.8
(90) Cobalt iodide (0.31 g, 1.0 mmol), adamantyl isocyanide (0.65 g, 4.0 mmol), THF (15 mL), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 0.27 g, 2.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in toluene (approximately 20 mL), and celite filtration was performed again. The solvent of the filtrate was distilled under reduced pressure, and then the dried substance was washed with a small amount of benzene (approximately 3 mL); thus, Co.sub.2(CNAd).sub.8 was obtained (0.33 g, 47%). .sup.1H-NMR spectrum of the resulting complex is shown in
(91) .sup.1H-NMR (396 MHz, C.sub.6D.sub.6) δ: 2.32 (s, 48H), 2.06 (s, 24H), 1.71 (d, J=10.3, 24H), 1.58 (d, J=10.3, 24H).
(92) IR (ATR): ν=1647 (CN (bridge)), 2101, 2000, 1954 (CN (terminal)) cm.sup.−1
(93) Anal. Calcd. for Ca.sub.88H.sub.120N.sub.8Co.sub.2: C, 75.08; H, 8.59; N, 7.96 Found: C, 75.16; H, 8.62; N, 7.46.
[Example 6] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CNMes).SUB.8 .Using Cobalt Iodide and KC.SUB.8
(94) Cobalt iodide (13 mg, 0.10 mmol), mesityl isocyanide (58 mg, 0.40 mmol), THF (3 mL), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in toluene (approximately 3 mL), and the insoluble matter was removed by celite filtration. Pentane (approximately 3 mL) was slowly added from above the filtrate to perform recrystallization; thus, a cobalt isocyanide complex of Co.sub.2 (CNMes).sub.8 was obtained (42 mg, yield: 66%). .sup.1H-NMR spectrum of the resulting complex is shown in
(95) .sup.1H-NMR (396 MHz, C.sub.6D.sub.6) δ: 6.60 (s, 12H), 6.58 (s, 4H), 2.46 (s, 36H), 2.42 (s, 12H), 2.05 (s, 18H), 2.03 (s, 6H).
(96) IR (ATR): ν=1669 (CN (bridge)), 2063, 2026, 1954 (CN (terminal)) cm.sup.−1
(97) Anal. Calcd. for C.sub.80H.sub.88N.sub.8Co.sub.2: C, 75.10; H, 6.93; N, 8.60 Found: C, 75.21; H, 6.90; N, 8.60.
[Example 7] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Iodide and Na Silica Gel (Stage I)
(98) Cobalt iodide (0.31 g, 1.0 mmol), THF (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), and Na silica gel (manufactured by Aldrich Corporation, Stage I, 0.34 g, 5.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 40 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (0.19 g, yield: 48%).
[Example 8] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Iodide and Na Silica Gel (Stage II)
(99) Cobalt iodide (0.31 g, 1.0 mmol), THF (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), and Na silica gel (manufactured by Aldrich Corporation, Stage II, 0.34 g, 5.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 40 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (13.9 mg, yield: 4%).
[Example 9] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt Iodide and NaK.SUB.2 .Silica Gel (Stage I)
(100) Cobalt iodide (0.31 g, 1.0 mmol), THF (15 mL), t-butyl isocyanide (0.33 g, 4.0 mmol), and NaK.sub.2 silica gel (manufactured by Aldrich Corporation, Stage I, 0.41 g, 5.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 40 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (120 mg, yield: 31%).
[Example 10] Synthesis of Iron Isocyanide Complex Fe(CN.SUP.t.Bu).SUB.5 .Using Iron Bromide and KC.SUB.8
(101) Iron bromide (22 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (42 mg, 0.50 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Fe(CN.sup.tBu).sub.5 was obtained (30 mg, yield: 63%). .sup.1H-NMR spectrum of the resulting complex is shown in
(102) .sup.1H-NMR (600 MHz, C.sub.6D.sub.6) δ: 1.29 (s, 45H).
(103) IR (ATR): ν=2119, 2000, 1943, 1826 (CN) cm.sup.−1
[Example 11] Synthesis of Iron Isocyanide Complex Fe(CNAd).SUB.5 .Using Iron Bromide and KC.SUB.8
(104) Iron bromide (216 mg, 1.0 mmol), THF (20 mL), adamantyl isocyanide (806 mg, 5.0 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 270 mg, 2.0 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in benzene (approximately 5 mL), and the insoluble matter was removed by celite filtration. Pentane was added to the filtrate, and then cooling was performed to −35° C. to perform recrystallization; thus, Fe(CNAd).sub.5 was obtained (601 mg, yield: 70%). .sup.1H-NMR spectrum of the resulting complex is shown in
(105) .sup.1H-NMR (396 MHz, C.sub.6D.sub.6) δ: 2.15 (s, 30H), 1.88 (s, 15H), 1.50 (d, J=11.5, 15H), 1.42 (d, J=11.5, 15H). IR (ATR): ν=2106 (CN) cm.sup.−1
[Example 12] Synthesis of Iron Isocyanide Complex Fe(CNMes).SUB.5 .Using Iron Bromide and KC.SUB.8
(106) Iron bromide (22 mg, 0.10 mmol), THF (3 mL), mesityl isocyanide (73 mg, 0.50 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 12 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in toluene (approximately 3 mL), and the insoluble matter was removed by celite filtration. Pentane (approximately 3 mL) was slowly added from above the filtrate to perform recrystallization; thus, Fe(CNMes).sub.5 was obtained (18 mg, yield: 23%). .sup.1H-NMR spectrum of the resulting complex is shown in
(107) .sup.1H-NMR (600 MHz, C.sub.6D.sub.6) δ: 6.60 (s, 10H), 2.48 (s, 30H), 2.05 (s, 15H).
(108) IR (ATR): ν=1971, 1940 (CN) cm.sup.−1
[Example 13] Synthesis of Nickel Isocyanide Complex Ni (CN.SUP.t.Bu).SUB.4 .Using Nickel Bromide (Dimethoxyethane Adduct) and KC.SUB.8
(109) Nickel bromide (a dimethoxyethane adduct) (31 mg, 0.1 mmol), THF (3 mL), t-butyl isocyanide (0.33 g, 0.4 mmol), and KC.sub.8 (270 mg, 2.0 mmol) were added in this order to a reactor, and stirring was performed at room temperature for 30 minutes. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in benzene (approximately 5 mL), and the insoluble matter was removed by celite filtration. Ether was added to the filtrate, and then cooling was performed to −35° C. to perform recrystallization; thus, Ni(CN.sup.tBu).sub.4 was obtained (21 mg, yield: 54%). .sup.1H-NMR spectrum of the resulting complex is shown in
(110) .sup.1H-NMR (396 MHz, C.sub.6D.sub.6) δ: 1.09 (s, 36H).
(111) IR (ATR): ν=2002 (CN) cm.sup.−1
[Example 14] Synthesis of Palladium Isocyanide Complex Pd.SUB.3.(CNMes).SUB.6 .Using Palladium Chloride and KC.SUB.8
(112) Palladium chloride (18 mg, 0.10 mmol), THF (3 mL), and mesityl isocyanide (29 mg, 0.20 mmol) were added to a reactor, and stirring was performed at 60° C. for 1 hour. Next, KC.sub.8 (27 mg, 0.20 mmol) was added, and stirring was performed at room temperature for 30 minutes. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was cleaned with ether (approximately 2 mL) twice; thus, Pd.sub.3(CNMes).sub.6 was obtained (25 mg, yield: 63%). .sup.1H-NMR spectrum of the complex is shown in
(113) .sup.1H-NMR (600 MHz, C.sub.6D.sub.6) δ: 6.45 (br, 10H), 2.29 (br, 30H), 1.87 (s, 15H).
(114) IR (ATR): ν=2089, 1979, 1755 (CN) cm.sup.−1
[Example 15] Synthesis of Pt-isocyanide Complex Using Platinum Chloride and KC.SUB.8
(115) Platinum chloride (27 mg, 0.10 mmol), THF (3 mL), and mesityl isocyanide (29 mg, 0.20 mmol) were added to a reactor, and stirring was performed at room temperature for 1 hour. Next, KC.sub.8 (27 mg, 0.20 mmol) was added, and stirring was performed at room temperature for 30 minutes. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in toluene (approximately 5 mL), and the insoluble matter was removed by celite filtration. Next, the solvent of the filtrate was distilled under reduced pressure, the resulting dried substance was dissolved in diethyl ether (approximately 1 mL), and the insoluble matter was removed by celite filtration again. The filtrate was cooled at −30° C. to perform recrystallization; thus, a Pt-isocyanide complex was obtained (7.7 mg, yield: 16%). .sup.1H-NMR spectrum of the resulting complex is shown in
(116) IR (ATR): ν=2087, 1649, 1603 (CN) cm.sup.−1
[Example 16] Synthesis of Rhodium Isocyanide Complex Rh.SUB.2.(CNMes).SUB.8 .Using chloro(1,5-cyclooctadiene)rhodium(I) dimers and KC.SUB.8
(117) Chloro(1,5-cyclooctadiene)rhodium(I) dimers (25 mg, 0.05 mmol), mesityl isocyanide (58 mg, 0.40 mmol), THF (3 mL), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 14 mg, 0.10 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 1 hour. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in benzene (approximately 3 mL), and pentane (approximately 10 mL) was added from above the filtrate to perform reprecipitation; thus, a rhodium isocyanide complex of Rh.sub.2(CNMes).sub.8 was obtained (11 mg, yield: 16%). .sup.1H-NMR spectrum of the resulting complex is shown in
(118) .sup.1H-NMR (396 MHz, C.sub.6D.sub.6) δ: 6.57 (br, 16H), 2.44 (br, 48H), 2.01 (br, 24H).
(119) IR (ATR): ν=1645, 1601 (CN (bridge)), 2051 (CN (terminal)) cm.sup.−1
[Example 17] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using bis(2,4-pentanedionato) Cobalt (II) and KC.SUB.8
(120) Bis (2,4-pentanedionato) cobalt (II) (26 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (33 mg, 0.40 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (6 mg, 15%).
[Example 18] Synthesis of Cobalt Isocyanide Complex Co.SUB.2.(CN.SUP.t.Bu).SUB.8 .Using Cobalt (II) Isopropoxide and KC.SUB.8
(121) Cobalt (II) isopropoxide (18 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (33 mg, 0.40 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Co.sub.2(CN.sup.tBu).sub.8 was obtained (3 mg, 8%).
[Example 19] Synthesis of Iron Isocyanide Complex Fe(CN.SUB.t.Bu).SUB.5 .Using Iron (II) Trifluoromethanesulfonate and KC.SUB.8
(122) Iron (II) trifluoromethanesulfonate (35 mg, 0.10 mmol), THF (3 mL), t-butyl isocyanide (42 mg, 0.50 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Fe(CN.sup.tBu).sub.5 was obtained (11 mg, 23%).
[Example 20] Synthesis of Molybdenum Isocyanide Complex Mo(CN.SUP.t.Bu).SUB.6 .Using Molybdenum Acetate (II) Dimer and KC.SUB.8
(123) Molybdenum acetate (II) dimer (21 mg, 0.05 mmol), THF (3 mL), t-butyl isocyanide (50 mg, 0.60 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 27 mg, 0.20 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Mo(CN.sup.tBu).sub.6 was obtained (3 mg, 2%). .sup.1H-NMR spectrum of the resulting complex is shown in
(124) .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) δ: 1.33 (s, 54H).
(125) IR (ATR): ν=2101, 1959 (CN) cm.sup.−1
[Example 21] Synthesis of Ruthenium Isocyanide Complex Ru(CN.SUB.t.Bu).SUB.5 .Using Ru.SUB.2.(OAc).SUB.4.Cl and KC.SUB.8
(126) Ru.sub.2(OAc).sub.4Cl (22 mg, 0.05 mmol), THF (3 mL), t-butyl isocyanide (42 mg, 0.50 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 34 mg, 0.25 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, Ru(CN.sup.tBu).sub.5 was obtained (5 mg, 10%). .sup.1H-NMR spectrum of the resulting complex is shown in
(127) .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) δ: 1.27 (s, 45H).
(128) IR (ATR): ν=2070, 2034, 1815 (CN) cm.sup.−1
[Example 22] Synthesis of Tungsten Chloride Complex W(CN.SUP.t.Bu).SUB.6 .Using Tungsten Chloride (IV) and KC.SUB.8
(129) Tungsten chloride (IV) (33 mg, 0.05 mmol), THF (3 mL), t-butyl isocyanide (50 mg, 0.60 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 54 mg, 0.50 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was dissolved in pentane (approximately 4 mL), and the insoluble matter was removed by celite filtration. The filtrate was cooled to −35° C. to perform recrystallization; thus, W(CN.sup.tBu).sub.6 was obtained (10 mg, 15%). .sup.1H-NMR spectrum of the resulting complex is shown in
(130) .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) δ: 1.34 (s, 54H).
(131) IR (ATR): ν=1960 (CN) cm.sup.−1
[Example 23] Synthesis of Vanadium Isocyanide Complex V(CN.SUP.t.Bu).SUB.6 .Using Vanadium(III) Bromide and KC.SUB.8
(132) Vanadium(III) bromide (33 mg, 0.05 mmol), THF (3 mL), t-butyl isocyanide (50 mg, 0.60 mmol), and KC.sub.8 (manufactured by Strem Chemicals, Inc., 41 mg, 0.30 mmol) were added in this order to a reactor, and stirring was performed at 25° C. for 3 hours. After that, the reaction solution was subjected to celite filtration, and the solvent of the filtrate was distilled under reduced pressure. The resulting dried substance was extracted by pentane (approximately 4 mL); thus, 9 mg of a crude product containing V(CN.sup.tBu).sub.6 was obtained. .sup.1H-NMR spectrum of the resulting crude product is shown in
(133) .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) δ: 1.38 (s, 54H).